Disclosed are ionically conductive membranes for protection of active metal anodes and methods for their fabrication. The membranes may be incorporated in active metal negative electrode (anode) structures and battery cells. In accordance with the invention, the membrane has the desired properties of high overall ionic conductivity and chemical stability towards the anode, the cathode and ambient conditions encountered in battery manufacturing. The membrane is capable of protecting an active metal anode from deleterious reaction with other battery components or ambient conditions while providing a high level of ionic conductivity to facilitate manufacture and/or enhance performance of a battery cell in which the membrane is incorporated.
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1. An electrochemical device component, comprising:
an active metal electrode having a first surface and a second surface; and
a protective membrane on the first surface of the electrode and having a smooth gap-free interface therewith, the membrane being ionically conductive and chemically compatible with the active metal on a side in contact with the active metal electrode, and substantially impervious, ionically conductive and chemically compatible with active metal corrosive environments on the other side;
wherein the ionic conductivity of the membrane is at least 10−5 S/cm; and
wherein the protective membrane comprises a composite, the composite comprising,
a first material in contact with the electrode, the first material being ionically conductive and chemically compatible with the active metal, wherein the first material comprises a composite reaction product of li with Cu3N, and
a second material in contact with the first material, the second material being substantially impervious, ionically conductive and chemically compatible with the first material and active metal corrosive environments, the second material selected from the group consisting of glassy or amorphous metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors,
wherein the ionic conductivity of the composite is at least 10−5 S/cm.
11. An electrochemical device component, comprising:
an active metal electrode having a first surface and a second surface; and
a protective membrane on the first surface of the electrode and having a smooth gap-free interface therewith, the membrane being ionically conductive and chemically compatible with the active metal on a side in contact with the active metal electrode, and substantially impervious, ionically conductive and chemically compatible with active metal conosive environments on the other side;
wherein the ionic conductivity of the membrane is at least 10−5 S/cm; and
wherein the protective membrane comprises a composite, the composite comprising,
a first material in contact with the electrode, the first material being ionically conductive and chemically compatible with the active metal, wherein the first material comprises a composite reaction product of the active metal with copper nitride (Cu3N), and
a second material in contact with the first material, the second material being substantially impervious, ionically conductive and chemically compatible with the first material and active metal corrosive environments, the second material selected from the group consisting of glassy or amorphous metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors,
wherein the ionic conductivity of the composite is at least 10−5 S/cm.
2. The component of
3. The component of
5. The component of
6. The component of
7. The component of
and containing a predominant crystalline phase composed of li1+x(M,Al,Ga)x(Ge1−yTiy)2−x(PO4)3 where X≦0.8 and 0≦Y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and li1+x+yQxTi2−xSiyP3−yO12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga.
8. The component of
and containing a predominant crystalline phase composed of li1+x(M,Al,Ga)x(Ge1−yTiy)2−x(PO4)3 where X≦0.8 and 0≦Y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and li1+x+YQxTi2−xSiyP3−yO12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga in a solid polymer electrolyte.
9. The component of
10. The component of
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This application is a continuation-in-part of U.S. patent application Ser. No. 10/731,771 filed Dec. 5, 2003, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, now U.S. Pat. No. 7,282,302, issued Oct. 16, 2007 which is a continuation-in-part of U.S. patent application Ser. No. 10/686,189 filed Oct. 14, 2003, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, now U.S. Pat. No. 7,282,296, issued Oct. 16, 2007 which claims priority to U.S. Provisional Patent Application No. 60/418,899 filed Oct. 15, 2002, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ANODES AND ELECTROLYTES.
This application also claims priority to U.S. Provisional Patent Application No. 60/511,710 filed Oct. 14, 2003, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ELECTRODES IN CORROSIVE ENVIRONMENTS and U.S. Provisional Patent Application No. 60/518,948 filed Nov. 10, 2003, titled BI-FUNCTINALLY COMPATIBLE IONICALLY COMPOSITES FOR ISOLATION OF ACTIVE METAL ELECTRODES IN A VARIETY OF ELECTROCHEMICAL CELLS AND SYSTEMS.
Each of these prior applications is incorporated herein by reference in its entirety and for all purposes.
1. Field of the Invention
The present invention relates generally to separators and electrode structures for use in batteries. More particularly, this invention relates to ionically conductive membranes for protection of active metal anodes from deleterious reaction with air, moisture and other battery components, battery cells incorporating such protected anodes and methods for their fabrication.
2. Description of Related Art
The low equivalent weight of alkali metals, such as lithium, render them particularly attractive as a battery electrode component. Lithium provides greater energy per volume than the traditional battery standards, nickel and cadmium. Unfortunately, no rechargeable lithium metal batteries have yet succeeded in the market place.
The failure of rechargeable lithium metal batteries is largely due to cell cycling problems. On repeated charge and discharge cycles, lithium “dendrites” gradually grow out from the lithium metal electrode, through the electrolyte, and ultimately contact the positive electrode. This causes an internal short circuit in the battery, rendering the battery unusable after a relatively few cycles. While cycling, lithium electrodes may also grow “mossy” deposits which can dislodge from the negative electrode and thereby reduce the battery's capacity.
To address lithium's poor cycling behavior in liquid electrolyte systems, some researchers have proposed coating the electrolyte facing side of the lithium negative electrode with a “protective layer.” Such protective layer must conduct lithium ions, but at the same time prevent contact between the lithium electrode surface and the bulk electrolyte. Many techniques for applying protective layers have not succeeded.
Some contemplated lithium metal protective layers are formed in situ by reaction between lithium metal and compounds in the cell's electrolyte which contact the lithium. Most of these in situ films are grown by a controlled chemical reaction after the battery is assembled. Generally, such films have a porous morphology allowing some electrolyte to penetrate to the bare lithium metal surface. Thus, they fail to adequately protect the lithium electrode.
Various pre-formed lithium protective layers have been contemplated. For example, U.S. Pat. No. 5,314,765 (issued to Bates on May 24, 1994) describes an ex situ technique for fabricating a lithium electrode containing a thin layer of sputtered lithium phosphorus oxynitride (“LiPON”) or related material. LiPON is a glassy single ion conductor (conducts lithium ion) which has been studied as a potential electrolyte for solid state lithium microbatteries that are fabricated on silicon and used to power integrated circuits (See U.S. Pat. Nos. 5,597,660, 5,567,210, 5,338,625, and 5,512,147, all issued to Bates et al.).
Work in the present applicants' laboratories has developed technology for the use of glassy or amorphous protective layers, such as LiPON, in active metal battery electrodes. (See, for example, U.S. Pat. No. 6,025,094, issued Feb. 15, 2000, U.S. Pat. No. 6,402,795, issued Jun. 11, 2002, U.S. Pat. No. 6,214,061, issued Apr. 10, 2001 and U.S. Pat. No. 6,413,284, issued Jul. 02, 2002, all assigned to PolyPlus Battery Company). Despite this progress, alternative protective layers and structures that could also enhance active metal, particularly lithium metal, battery performance continue to be sought. In particular, protective layers that combine the characteristics of high ionic conductivity and chemical stability to materials and conditions on either side of the protective layer are desired.
The present invention provides ionically conductive membranes for decoupling the active metal anode and cathode sides of an active metal electrochemical cell, and methods for their fabrication. The membranes may be incorporated in active metal negative electrode (anode) structures and electrochemical devices and components, including battery and fuel cells. The membranes are highly conductive for ions of the active metal, but are otherwise substantially impervious. They are chemically stable on one side to the active metal of the anode (e.g., lithium), and on the other side to the cathode, other battery cell components such as solid or liquid phase electrolytes, including organic or aqueous liquid electrolytes, ambient conditions and other environments corrosive to the active metal of the anode if directly contacted with it. The membrane is capable of protecting an active metal anode from deleterious reaction with other battery components or ambient conditions and decoupling the chemical environments of the anode and cathode enabling use of anode-incompatible materials, such as solvents and electrolytes, on the cathode side without deleterious impact on the anode, and vice versa. This broadens the array of materials that may be used in active metal electrochemical cells and facilitates cell fabrication while providing a high level of ionic conductivity to enhance performance of an electrochemical cell in which the membrane is incorporated.
The membrane may have any suitable composition, for example, it may be a monolithic material chemically compatible with both the anode and cathode environments, or a composite composed of at least two components of different materials having different chemical compatibilities, one chemically compatible with the anode environment and the other chemically compatible with the cathode environment.
Composite membranes may be composed of a laminate of discrete layers of materials having different chemical compatibility requirements, or it may be composed of a gradual transition between layers of the materials. By “chemical compatibility” (or “chemically compatible”) it is meant that the referenced material does not react to form a product that is deleterious to battery cell operation when contacted with one or more other referenced battery cell components or manufacturing, handling or storage conditions. A first material layer (or first layer material) of the composite is ionically conductive, and chemically compatible with an active metal electrode material. Chemical compatibility in this aspect of the invention refers both to a material that is chemically stable and therefore substantially unreactive when contacted with an active metal electrode material. It may also refer to a material that is chemically stable with air, to facilitate storage and handling, and reactive when contacted with an active metal electrode material to produce a product that is chemically stable against the active metal electrode material and has the desirable ionic conductivity (i.e., a first layer material). Such a reactive material is sometimes referred to as a “precursor” material. A second material layer of the composite is substantially impervious, ionically conductive and chemically compatible with the first material. Additional layers are possible to achieve these aims, or otherwise enhance electrode stability or performance. All layers of the composite have high ionic conductivity, at least 10−7 S/cm, generally at least 10−6 S/cm, for example at least 10−5 S/cm to 10−4 S/cm, and as high as 10−3 S/cm or higher so that the overall ionic conductivity of the multi-layer protective structure is at least 10−7 S/cm and as high as 10−3 S/cm or higher.
A wide variety of materials may be used in fabricating protective composites in accordance with the present invention, consistent with the principles described above. For example, the first layer, in contact with the active metal, may be composed, in whole or in part, of active metal nitrides, active metal phosphides, active metal halides or active metal phosphorus oxynitride-based glass. Specific examples include Li3N, Li3P, LiI, LiBr, LiCl, LiF and LiPON. Active metal electrode materials (e.g., lithium) may be applied to these materials, or they may be formed in situ by contacting precursors such as metal nitrides, metal phosphides, metal halides, red phosphorus, iodine, nitrogen or phosphorus containing organics and polymers, and the like with lithium. The in situ formation of the first layer may result from an incomplete conversion of the precursors to their lithiated analog. Nevertheless, such incomplete conversions meet the requirements of a first layer material for a protective composite in accordance with the present invention and are therefore within the scope of the invention.
A second layer of the protective composite may be composed of a material that is substantially impervious, ionically conductive and chemically compatible with the first material or precursor and environments normally corrosive to the active metal of the anode, including glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulpher-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass (such as are described D. P. Button et al., Solid State Ionics, Vols. 9-10, Part 1, 585-592 (December 1983); ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), and the like; or glass-ceramic active metal ion conductors. Specific examples include LiPON, Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3, Li2O.11Al2O3, Na2O.11Al2O3, (Na, Li)1+xTi2−xAlx(PO4)3 (0.6≦x≦0.9) and crystallographically related structures, Na3Zr2Si2PO12, Li3Zr2Si2PO12, Na5ZrP3O12, Na5TiP3O12, Na3Fe2P3O12, Na4NbP3O12,Li5ZrP3O12, Li5TiP3O12, Li3Fe2P3O12 and Li4NbP3O12, and combinations thereof, optionally sintered or melted. Suitable ceramic ion active metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety and for all purposes.
A particularly suitable glass-ceramic material for the second layer of the protective composite is a lithium ion conductive glass-ceramic having the following composition:
Composition
mol %
P2O5
26-55%
SiO2
0-15%
GeO2 + TiO2
25-50%
in which GeO2
0-50%
TiO2
0-50%
ZrO2
0-10%
M2O3
0 < 10%
Al2O3
0-15%
Ga2O3
0-15%
Li2O
3-25%
and containing a predominant crystalline phase composed of Li1+x(M,Al,Ga)x(Ge 1−yTiy)2−x(PO4)3 where X≦0.8 and 0≦Y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and Li1+x+yQxTi2−xSiyP3−yO12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga. The glass-ceramics are obtained by melting raw materials to a melt, casting the melt to a glass and subjecting the glass to a heat treatment. Such materials are available from OHARA Corporation, Japan and are further described in U.S. Pat. Nos. 5,702,995, 6,030,909, 6,315,881 and 6,485,622, incorporated herein by reference.
Either layer may also include additional components. For instance, a suitable active metal compatible layer (first layer) may include a polymer component to enhance its properties. For example, polymer-iodine complexes like poly(2-vinylpyridine)-iodine (P2VP-I2), polyethylene-iodine, or tetraalkylammonium-iodine complexes can react with Li to form a LiI-based film having significantly higher ionic conductivity than that for pure LiI. Also, a suitable first layer may include a material used to facilitate its use, for example, the residue of a wetting layer (e.g., Ag) used to prevent reaction between vapor phase lithium (during deposition) and LiPON when LiPON is used as a first layer material.
In solid state embodiments, a suitable second layer may include a polymer component to enhance its properties. For example, a glass-ceramic active metal ion conductor, like the glass-ceramic materials described above, may also be combined with polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite. One important example of such a flexible composite material has been developed by OHARA Corp. (Japan). It is composed of particles of a Li-ion conducting glass-ceramic material, such as described above, and a solid polymer electrolyte based on PEO-Li salt complexes. OHARA Corp. manufactures this material in the form of sheet with a thickness of about 50 microns that renders it flexible while maintaining its high ionic conductivity. Because of its relatively high ionic conductivity (better than 4*10−5 S/cm at room temperature in the case of the OHARA product) and stability toward metallic Li, this type of composite electrolyte can be used at room temperature or elevated temperatures in fully solid-state cells.
In addition, the layers may be formed using a variety of techniques. These include deposition or evaporation (including e-beam evaporation) of layers of material, such as Li3N or an ionically conductive glass. Also, as noted above, the active metal electrode adjacent layer may be formed in situ from the non-deleterious reaction of one or more precursors with the active metal electrode. For example, a Li3N layer may be formed on a Li anode by contacting Cu3N with the Li anode surface, or Li3P may be formed on a Li anode by contacting red phosphorus with the Li anode surface.
The invention encompasses protected anode structures with fully-formed protective layers and battery separators incorporating ambient stable precursors, each of which may be handled or stored in normal ambient atmospheric conditions without degradation prior to incorporation into a battery cell. Battery cells and methods for making composites and battery cells are also provided.
These and other features of the invention are further described and exemplified in the detailed description below.
Reference will now be made in detail to specific embodiments of the invention. Examples of the specific embodiments are illustrated in the accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail in order not to unnecessarily obscure the present invention.
When used in combination with “comprising,” “a method comprising,” “a device comprising” or similar language in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs.
Introduction
The present invention provides ionically conductive membranes for decoupling the active metal anode and cathode sides of an active metal electrochemical cell, and methods for their fabrication. The membranes may be incorporated in active metal negative electrode (anode) structures and electrochemical devices and components, including battery and fuel cells. The membranes are highly conductive for ions of the active metal, but are otherwise substantially impervious. They are chemically stable on one side to the active metal of the anode (e.g., lithium), and on the other side to the cathode, other battery cell components such as solid or liquid phase electrolytes, including organic or aqueous liquid electrolytes, and preferably to ambient conditions. The membrane is capable of protecting an active metal anode from deleterious reaction with other battery components or ambient conditions and decoupling the chemical environments of the anode and cathode enabling use of anode-incompatible materials, such as solvents and electrolytes, on the cathode side without deleterious impact on the anode, and vice versa. This broadens the array of materials that may be used in active metal electrochemical cells and facilitates cell fabrication while providing a high level of ionic conductivity to enhance performance of an electrochemical cell in which the membrane is incorporated.
The membrane may have any suitable composition, for example, it may be a monolithic material chemically compatible with both the anode and cathode environments, or a composite composed of at least two components of different materials having different chemical compatibilities, one chemically compatible with the anode environment and the other chemically compatible with the cathode environment.
Composite membranes may be composed of at least two components of different materials having different chemical compatibility requirements. The composite may be composed of a laminate of discrete layers of materials having different chemical compatibility requirements, or it may be composed of a gradual transition between layers of the materials. By “chemical compatibility” (or “chemically compatible”) it is meant that the referenced material does not react to form a product that is deleterious to battery cell operation when contacted with one or more other referenced battery cell components or manufacturing, handling or storage conditions.
A first material layer of the composite is both ionically conductive and chemically compatible with an active metal electrode material. Chemical compatibility in this aspect of the invention refers to a material that is chemically stable and therefore substantially unreactive when contacted with an active metal electrode material. Active metals are highly reactive in ambient conditions and can benefit from a barrier layer when used as electrodes. They are generally alkali metals such (e.g., lithium, sodium or potassium), alkaline earth metals (e.g., calcium or magnesium), and/or certain transitional metals (e.g., zinc), and/or alloys of two or more of these. The following active metals may be used: alkali metals (e.g., Li, Na, K), alkaline earth metals (e.g., Ca, Mg, Ba), or binary or ternary alkali metal alloys with Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In. Preferred alloys include lithium aluminum alloys, lithium silicon alloys, lithium tin alloys, lithium silver alloys, and sodium lead alloys (e.g., Na4Pb). A preferred active metal electrode is composed of lithium. Chemical compatibility also refers to a material that may be chemically stable with oxidizing materials and reactive when contacted with an active metal electrode material to produce a product that is chemically stable against the active metal electrode material and has the desirable ionic conductivity (i.e., a first layer material). Such a reactive material is sometimes referred to as a “precursor” material.
A second material layer of the composite is substantially impervious, ionically conductive and chemically compatible with the first material. By substantially impervious it is meant that the material provides a sufficient barrier to battery electrolytes and solvents and other battery component materials that would be damaging to the electrode material to prevent any such damage that would degrade electrode performance from occurring. Thus, it should be non-swellable and free of pores, defects, and any pathways allowing air, moisture, electrolyte, etc. to penetrate though it to the first material. Preferably, the second material layer is so impervious to ambient moisture, carbon dioxide, oxygen, etc. that an encapsulated lithium alloy electrode can be handled under ambient conditions without the need for elaborate dry box conditions as typically employed to process other lithium electrodes. Because the composite protective layer described herein provides such good protection for the lithium (or other active metal), it is contemplated that electrodes and electrode/electrolyte composites of this invention may have a quite long shelf life outside of a battery. Thus, the invention contemplates not only batteries containing a negative electrode, but unused negative electrodes and electrode/electrolyte laminates themselves. Such negative electrodes and electrode/electrolyte laminates may be provided in the form of sheets, rolls, stacks, etc. Ultimately, they may be integrated with other battery components to fabricate a battery. The enhanced stability of the batteries of this invention will greatly simplify this fabrication procedure.
In addition to the protective composite laminate structure described above, a protective composite in accordance with the present invention may alternatively be a functionally graded layer, as further described below.
It should be noted that the first and second materials are inherently ionically conductive. That is, they do not depend on the presence of a liquid electrolyte or other agent for their ionically conductive properties.
Additional layers are possible to achieve these aims, or otherwise enhance electrode stability or performance. All layers of the composite have high ionic conductivity, at least 10−7 S/cm, generally at least 10−6 S/cm, for example at least 10−5 S/cm to 10−4 S/cm, and as high as 10−3 S/cm or higher so that the overall ionic conductivity of the multi-layer protective structure is at least 10−7 S/cm and as high as 10−3 S/cm or higher.
Protective Membranes and Structures
The protective membrane may be a composite composed of two or more materials that present sides having different chemical compatibility to the anode and electrolyte and/or cathode, respectively. The composite is composed of a first layer of a material that is both ionically conductive and chemically compatible with an active metal electrode material. The composite also includes second layer of a material that is substantially impervious, ionically conductive and chemically compatible with the first material and the cathode/electrolyte environment.
As described further below, given the protection afforded by the protective membranes of the present invention, the electrolytes and/or cathodes combined with the protected anodes of the present invention may include a wide variety of materials including, but not limited to, those described in the patents of PolyPlus Battery Company, referenced herein below.
As noted above, the first material may also be a precursor material which is chemically compatible with an active metal and reactive when contacted with an active metal electrode material to produce a product that is chemically stable against the active metal electrode material and has the desirable ionic conductivity (i.e., a first layer material). Examples of suitable precursor materials include metal nitrides, red phosphorus, nitrogen and phosphorus containing organics (e.g., amines, phosphines, borazine (B3N3H6), triazine (C3N3H3)) and halides. Some specific examples include P (red phosphorus), Cu3N, SnNx, Zn3N2, FeNx, CoNx, aluminum nitride (AIN), silicon nitride (Si3N4) and I2, Br2, Cl2 and F2. Such precursor materials can subsequently react with active metal (e.g., Li) to form a Li metal salts, such as the lithium nitrides, phosphides and halides described above. In some instances, these first layer material precursors may also be chemically stable in air (including moisture and other materials normally present in ambient atmosphere), thus facilitating handling and fabrication. Examples include metal nitrides, for example Cu3N.
Also, a suitable active metal compatible layer may include a polymer component to enhance its properties. For example, polymer-iodine complexes like poly(2-vinylpyridine)-iodine (P2VP-I2), polyethylene-iodine, or with tetraalkylammonium-iodine complexes can react with Li to form a LiI-based film having significantly higher ionic conductivity than that for pure LiI.
The ionic conductivity of the first material is high, at least 10−7 S/cm, generally at least about 10−5 S/cm, and may be as high as 10−3 S/cm or higher.
Adjacent to the first material or precursor layer 202 is a second layer 204 that is substantially impervious, ionically conductive and chemically compatible with the first material or precursor, including glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulpher-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass (such as are described D.P. Button et al., Solid State Ionics, Vols. 9-10, Part 1, 585-592 (December 1983); ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), and the like; or glass-ceramic active metal ion conductors. Specific examples include LiPON, Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3, Li2O.11Al2O3, Na2O.11Al2O3, (Na, Li)1+xTi2−xAlx(PO4)3 (0.6≦x≦0.9) and crystallographically related structures, Na3Zr2Si2PO12, Li3Zr2Si2PO12, Na5ZrP3O12, Na5TiP3O12, Na3Fe2P3O12, Na4NbP3O12, Li5ZrP3O12, Li5TiP3O12, Li3Fe2P3O12 and Li4NbP3O12, and combinations thereof, optionally sintered or melted. Suitable ceramic ion active metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety and for all purposes.
A particularly suitable glass-ceramic material for the second layer of the protective composite is a lithium ion conductive glass-ceramic having the following composition:
Composition
mol %
P2O5
26-55%
SiO2
0-15%
GeO2 + TiO2
25-50%
in which GeO2
0-50%
TiO2
0-50%
ZrO2
0-10%
M2O3
0 < 10%
Al2O3
0-15%
Ga2O3
0-15%
Li2O
3-25%
and containing a predominant crystalline phase composed of Li1+x(M,Al,Ga)x(Ge 1−yTiy)2−x(PO4)3 where X≦0.8 and 0≦Y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm and Yb and/or and Li1+x+YQxTi2−xSiyP3−yO12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga. The glass-ceramics are obtained by melting raw materials to a melt, casting the melt to a glass and subjecting the glass to a heat treatment. Such materials are available from OHARA Corporation, Japan and are further described in U.S. Pat. Nos. 5,702,995, 6,030,909, 6,315,881 and 6,485,622, incorporated herein by reference.
The high conductivity of some of these glasses, ceramics and glass-ceramics (ionic conductivity in the range of about 10−5 to 10−3 S/cm or greater) may enhance performance of the protected lithium anode, and allow relatively thick films to be deposited without a large penalty in terms of ohmic resistance.
Also, for solid state applications, a suitable second layer may include a polymer component to enhance its properties. For example, a glass-ceramic active metal ion conductor, like the glass-ceramic materials described above, may also be combined with polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite. One important example of such a flexible composite material has been developed by OHARA Corp. (Japan). It is composed of particles of a Li-ion conducting glass-ceramic material, such as described above, and a solid polymer electrolyte based on PEO-Li salt complexes. OHARA Corp. manufactures this material in the form of sheet with a thickness of about 50 microns that renders it flexible while maintaining its high ionic conductivity. Because of its relatively high ionic conductivity (better than 4*10−5 S/cm at room temperature in the case of the OHARA product) and stability toward metallic Li, this type of composite electrolyte can be used at room temperature or elevated temperatures in fully solid-state cells.
The composite barrier layer should have an inherently high ionic conductivity. In general, the ionic conductivity of the composite is at least 10−7 S/cm, generally at least about 10−6 to 10−5 S/cm, and may be as high as 10−4 to S10−3/cm or higher. The thickness of the first precursor material layer should be enough to prevent contact between the second material layer and adjacent materials or layers, in particular, the active metal of the anode with which the separator is to be used. For example, the first material layer may have a thickness of about 0.1 to 5 microns; 0.2 to 1 micron; or about 0.25 micron.
The thickness of the second material layer is preferably about 0.1 to 1000 microns, or, where the ionic conductivity of the second material layer is about 10−7 S/cm, about 0.25 to 1 micron, or, where the ionic conductivity of the second material layer is between about 10−4 about 10−3 S/cm, about 10 to 1000 microns, preferably between 1 and 500 microns, and more preferably between 10 and 100 microns, for example 20 microns.
When the first material layer is a precursor material chemically stable in air, for example Cu3N or LiPON, the protective composite battery separator may be handled or stored in normal ambient atmospheric conditions without degradation prior to incorporation into a battery cell. When the separator is incorporated into a battery cell, the precursor layer 202 is contacted with an active metal (e.g., lithium) electrode. The precursor reacts with the active metal to form an ionically conductive material that is chemically compatible with the active metal electrode material. The second layer is contacted with an electrolyte to which a cathode and current collector is or has been applied. Alternatively, the second layer acts as the sole electrolyte in the battery cell. In either case, the combination of the two layers in the protective composite protects the active metal electrode and the electrolyte and/or cathode from deleterious reaction with one another.
In addition to the protective composite laminates described above, a protective composite in accordance with the present invention may alternatively be compositionally and functionally graded, as illustrated in
Active metal electrode materials (e.g., lithium) may be applied to these materials, or they may be formed in situ by contacting precursors such as metal nitrides, metal phosphides, metal halides, red phosphorus, iodine and the like with lithium. The in situ formation of the first layer may be by way of conversion of the precursors to a lithiated analog, for example, according to reactions of the following type (using P, CuN3, and PbI2 precursors as examples):
1. 3Li+P=Li3P (reaction of the precursor to form Li-ion conductor);
2(a). 3Li+Cu3N=Li3N+3 Cu (reaction to form Li-ion conductor/metal composite);
2(b). 2Li+PbI2=2 LiI+Pb (reaction to form Li-ion conductor/metal composite).
First layer composites, which may include electronically conductive metal particles, formed as a result of in situ conversions meet the requirements of a first layer material for a protective composite in accordance with the present invention and are therefore within the scope of the invention.
A second layer 306 of the protective composite is composed of a substantially impervious, ionically conductive and chemically compatible with the first material or precursor, including glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulpher-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass; ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), and the like; or glass-ceramic active metal ion conductors. Specific examples include LiPON, Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3, Li2O.11Al2O3, Na2O.11Al2O3, (Na, Li)1+xTi2−xAlx(PO4)3 (0.6≦x≦0.9) and crystallographically related structures, Na3Zr2Si2PO12, Li3Zr2Si2PO12, Na5ZrP3O12, Na5TiP3O12, Na3Fe2P3O12, Na4NbP3O12, Li5ZrP3O12, Li5TiP3O12,Li3Fe2P3O12 and Li4NbP3O12, and combinations thereof, optionally sintered or melted. Suitable ceramic ion active metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety and for all purposes. Suitable glass-ceramic ion active metal ion conductors are described, for example, in U.S. Pat. Nos. 5,702,995, 6,030,909, 6,315,881 and 6,485,622, previously incorporated herein by reference and are available from OHARA Corporation, Japan.
The ionic conductivity of the composite is at least 10−7 S/cm, generally at least 10−6 S/cm, for example at least 10−5 S/cm to 10−4 S/cm, and as high as 10−3 S/cm or higher. The thickness of the second material layer is preferably about 0.1 to 1000 microns, or, where the ionic conductivity of the second material layer is about 10−7 S/cm, about 0.25 to 1 micron, or, where the ionic conductivity of the second material layer is between about 10−4 about 10−3 S/cm, 10 to 1000 microns, preferably between 1 and 500 micron, and more preferably between 10 and 100 microns, for example 20 microns.
When the anode structure is incorporated in a battery cell, the first layer 304 is adjacent to an active metal (e.g., lithium) anode and the second layer 306 is adjacent to an electrolyte or, where the second layer is the sole electrolyte in the battery cell, a cathode.
Either layer may also include additional components. For instance, a suitable first active metal compatible layer 304 may include a polymer component to enhance its properties. For example, polymer-iodine complexes like poly(2-vinylpyridine)-iodine (P2VP-I2), polyethylene-iodine, or with tetraalkylammonium-iodine can react with Li to form a LiI-based film having significantly higher ionic conductivity than that for pure LiI. Also, for solid state applications, a suitable second layer 306 may include a polymer component to enhance its properties. For example, a glass-ceramic active metal ion conductor like that available from OHARA Corporation, described above, may be fabricated within a polymer matrix that renders it flexible while maintaining its high ionic conductivity (available from OHARA Corporation, Japan).
In addition, the layers may be formed using a variety of techniques. These include deposition or evaporation (including e-beam evaporation) of layers of material, such as LiN3 or an ionically conductive glass. Also, as noted above, the active metal electrode adjacent layer may be formed in situ from the non-deleterious reaction of one or more precursors with the active metal electrode. For example, a LiN3 layer may be formed on a Li anode by contacting CuN3 with the Li anode surface, or LiP3 may be formed on a Li anode by contacting red phosphorus with the Li anode surface.
As noted above with regard to the protective membrane separator structures described in connection with
As noted with reference to the graded separator in
Also, an approach may be used where a first material and second material are coated with another material such as a transient and/or wetting layer. For example, an OHARA glass ceramic plate is coated with a LiPON layer, followed by a thin silver (Ag) coating. When lithium is evaporated onto this structure, the Ag is converted to Ag—Li and diffuses, at least in part, into the greater mass of deposited lithium, and a protected lithium electrode is created. The thin Ag coating prevents the hot (vapor phase) lithium from contacting and adversely reaction with the LiPON first material layer. After deposition, the solid phase lithium is stable against the LiPON. A multitude of such transient/wetting (e.g., Sn) and first layer material combinations can be used to achieve the desired result.
Thus, the invention encompasses protected anode structures with fully-formed protective layers and battery separators incorporating ambient stable precursors, each of which may be handled or stored in normal ambient atmospheric conditions without degradation prior to incorporation into a battery cell. Battery cells and methods for making separators, anode structures and battery cells are also provided.
Battery Cells
Protected active metal anodes as described herein may be incorporated into a variety of battery cell structures. These includes fully solid state battery cells and battery cells with gel and liquid electrolyte systems, including, but not limited to, those described in the patents of PolyPlus Battery Company, referenced herein.
Solid and Gel State Batteries
A solid state battery cell in accordance with the present invention may include a protected anode as described herein against a polymer electrolyte such as polyethylene oxide (PEO), and a PEO/carbon/metal-oxide type cathode.
Alternatively, gel-state electrolytes in which non-aqueous solvents have been gelled through the use of a gelling agent such as polyacrylonitrile (PAN), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), or polymerizable monomers that are added to the non-aqueous solvent system and polymerized in situ by the use of heat or radiation may be used.
Examples of suitable solid and gel state electrolytes and batteries incorporating them are described, for example, in U.S. Pat. No. 6,376,123, issued Apr. 23, 2002 and titled RECHARGEABLE POSITIVE ELECTRODES, assigned to PolyPlus Battery Company, the assignee of the present application, which is incorporated herein by reference in its entirety and for all purposes.
Liquid Electrolytes
One of the main requirements of the liquid electrolyte system for all Li-metal and Li-ion battery cells is its compatibility with the anode material. The liquid electrolytes of existing Li-metal and Li-ion cells are not thermodynamically stable toward Li metal, Li alloys, and Li—C compounds, but rather kinetically stable due to formation of a solid electrolyte interface (SEI) protecting the anode surface from a continuous reaction with components of the electrolyte. Therefore, only a very limited spectrum of aprotic solvents and supporting salts is suitable for use in Li-metal and Li-ion batteries with an unprotected anode. In particular, the binary, ternary or multicomponent mixtures of alkyl carbonates or their mixtures with ethers are used as solvents, and LiPF6 is generally used as a supporting salt in electrolytes for Li-ion batteries.
The main component of these solvent mixtures is ethylene carbonate (EC). It has been shown that without the presence of EC in the electrolyte, the SEI formed does not provide enough protection for anode surface, and cell's cyclability is very poor. However, EC has a high melting point of 35° C. and a high viscosity that limits the rate capability and the cell's low temperature performance. Another important disadvantage of existing Li-ion batteries is the irreversible capacity loss during the first charge associated with in situ formation of the SEI.
Protection of the anode with an ionically conductive protective membrane in accordance with the present invention allows for use of a very wide spectrum of solvents and supporting salts in rechargeable and primary batteries with Li metal anodes. The protected anode is completely decoupled from the electrolyte, so electrolyte compatibility with the anode is no longer an issue; solvents and salts which are not kinetically stable to Li can be used. Improved performance can be obtained with conventional liquid electrolytes, as noted above and as described, for example, in U.S. Pat. No. 6,376,123, previously incorporated herein by reference. Moreover, the electrolyte solution can be composed of only low viscosity solvents, such as ethers like 1,2-dimethoxy ethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,3-dioxolane (DIOX), 4-methyldioxolane (4-MeDIOX) or organic carbonates like dimethylcarbonate (DMC), ethylmethylcarbonate (EMC), diethylcarbonate (DEC), or their mixtures. Also, super low viscosity ester solvents or co-solvents such as methyl formate and methyl acetate, which are very reactive to unprotected Li, can be used. As is known to those skilled in the art, ionic conductivity and diffusion rates are inversely proportional to viscosity such that all other things being equal, battery performance improves as the viscosity of the solvent decreases. The use of such electrolyte solvent systems significantly improves battery performance, in particular discharge and charge characteristics at low temperatures.
Ionic Liquids
Ionic liquids are organic salts with melting points under 100 degrees, often even lower than room temperature. The most common ionic liquids are imidazolium and pyridinium derivatives, but also phosphonium or tetralkylammonium compounds are also known. Ionic liquids have the desirable attributes of high ionic conductivity, high thermal stability, no measurable vapor pressure, and non-flammability. Representative ionic liquids are 1-Ethyl-3-methylimidazolium tosylate (EMIM-Ts), 1-Butyl-3-methylimidazolium octyl sulfate (BMIM-OctSO4), 1-Ethyl-3-methylimidazolium hexafluorophosphate, and 1-Hexyl-3-methylimidazolium tetrafluoroborate. Although there has been substantial interest in ionic liquids for electrochemical applications such as capacitors and batteries, they are unstable to metallic lithium and lithiated carbon. However, protected lithium anodes as described in this invention are isolated from direct chemical reaction, and consequently lithium metal batteries using ionic liquids can be developed as an embodiment of the present invention. Such batteries should be particularly stable at elevated temperatures.
Cathodes
Another important advantage associated with the use of ionically conductive protective membranes in accordance with the present invention in battery cells is that both lithiated intercalation compounds and unlithiated intercalation compounds can be used as cathode materials. As a result, protection of the anode with ionically conductive composite materials allows for use of a variety of 2, 3, 4 and 5 V cathodes suitable for fabrication of primary and rechargeable batteries for a wide range of applications. Examples of lithiated metal oxide based cathodes suitable for rechargeable cells with protected Li anodes in accordance with the present invention include: LixCoO2, LixNiO2, LixMn2O4 and LiFePO4. Examples of unlithiated metal oxide or sulfide based cathodes suitable for use both for primary and rechargeable cells with protected Li anodes in accordance with the present invention include: AgxV2O5, CuxV2O5, V2O5, V6O13, FeS2 and TiS2. Examples of metal oxide based cathodes suitable for primary cells with protected Li anodes in accordance with the present invention include: MnO2, CuO, Ag2CrO4 and MoO3. Examples of metal sulfide based positive electrodes for primary cells with protected Li anodes in accordance with the present invention include: CuS and FeS.
In addition, active sulfur cathodes including elemental sulfur and polysulfides, as described in the patents of PolyPlus Battery Company cited and incorporated by reference below are suitable cathodes for protected lithium metal anode battery cells in accordance with the present invention.
Fabrication Techniques
Materials and techniques fox fabrication of active metal battery cells are described, for example, in U.S. Pat. No. 5,686,201 issued to Chu on Nov. 11, 1997. Further description of materials and techniques for fabrication of active metal battery cells having anode protective layers are described, for example, in U.S. patent application Ser. No. 09/139,601, filed Aug. 25, 1998 (now U.S. Pat. No. 6,214,061, issued Apr. 10, 2001), titled ENCAPSULATED LITHIUM ALLOY ELECTRODES HAViNG BARRIER LAYERS, and naming May-Ying Chu, Steven J. Visco and Lutgard C. DeJonge as inventors; U.S. patent application Ser. No. 09/086,665 filed May 29, 1998 (now U.S. Pat. No. 6,025,094, issued May 15, 2000), titled PROTECTIVE COATINGS FOR NEGATIVE ELECTRODES, and naming Steven J. Visco and May-Ying Chu as inventors; U.S. patent application Ser. No. 09/139,603 filed Aug. 25, 1998 (now U.S. Pat. No. 6,402,795, issued Jun. 11, 2002), titled “PLATING METAL NEGATIVE ELECTRODES UNDER PROTECTIVE COATINGS,” and naming May-Ying Chu, Steven J. Visco and Lutgard C. DeJonghe as inventors; U.S. patent application Ser. No. 09/139,601 filed Aug. 25, 1998 (now U.S. Pat. No. 6,214,061, issued Apr. 10, 2001), titled “METHOD FOR FORMING ENCAPSULATED LITHIUM ELECTRODES HAVING GLASS PROTECTIVE LAYERS,” and naming Steven J. Visco and Floris Y. Tsang as inventors. The active metal electrode may also be an active metal alloy electrode, as further described in U.S. patent application Ser. No. 10/189,908 filed Jul. 3, 2002 (now U.S. Pat. No. 6.991,662, issued Jan. 31, 2006) titled “ENCAPSULATED ALLOY ELECTRODES,” and naming Steven J. Visco, Yevgeniy S. Nimon and Bruce D. Katz as inventors. The battery component materials, including anodes, cathodes, separators, protective layers, etc., and techniques disclosed therein are generally applicable in the present invention and each of these patent applications is incorporated herein by reference in its entirety for all purposes.
In particular, a protective membrane in accordance with the present invention may be formed using a variety of methods. These include deposition or evaporation. Protective membrane composites of the present invention may be formed by deposition or evaporation (including e-beam evaporation) of the first layer of material or precursor on the second layer of material. Also, as noted above and described further below, the first layer may be formed in situ from the non-deleterious reaction of one or more precursors with an active metal electrode or material, by deposition or evaporation of lithium on the precursor, by direct contact of the precursor with a lithium metal (e.g., foil), or by plating of the precursor with lithium through a second layer material. In some embodiments, the second layer material may also be formed on the first layer material, as described further below.
Referring to
Alternatively, referring to
In another alternative, illustrated in
To form a protected anode, lithium is then bonded to the graded membrane on the first layer material (stable to active metal) side of the graded protective composite, for example by evaporation of lithium onto the protective composite as described above. It may also be desirable to add a bonding layer on top of the lithium stable side of the graded composite protective layer, such as Sn, Ag, Al, etc., before applying lithium.
In any of the forgoing methods described with reference to
In a further embodiment, a suitable substrate, e.g., having a wetting layer, such as a film of tin on copper, may be coated with a first layer material precursor, e.g., Cu3N. This may then be coated with a second layer material, e.g., a (ionically) conductive glass. An active metal electrode may then be formed by plating the tin electrode with lithium (or other active metal), through the first and second layer materials. The Cu3N precursor is also converted to Li3N by this operation to complete the protective composite in accordance with the present invention on a lithium metal electrode. Details of an active metal plating process are described in commonly assigned U.S. Pat. No. 6,402,795, previously incorporated by reference.
With regard to the fabrication methods described above it is important to note that commercial lithium foils are typically extruded and have numerous surface defects due to this process, many of which have deep recesses that would be unreachable by line-of-sight deposition techniques such as RF sputter deposition, thermal and E-beam evaporation, etc. Another issue is that active metals such as lithium may be reactive to the thin-film deposition environment leading to further deterioration of the surface during the coating process. This typically leads to gaps and holes in a membrane deposited onto the surface of an active metal electrode. However, by inverting the process, this problem is avoided; lithium is deposited on the protective membrane rather than the protective membrane being deposited on lithium. Glass, and glass-ceramic membranes can be made quite smooth either by melt-casting techniques, cut and polish methods, or a variety of known methods leading to smooth surfaces (lithium is a soft metal that cannot be polished). Single or multiple smooth, gap-free membranes may then be deposited onto the smooth surface. After deposition is complete, active metal can be deposited onto the smooth surface by evaporation, resulting is a active meta/protective membrane interface that is smooth and gap-free. Alternatively, a transient bonding layer such as Ag can be deposited onto the protective membrane such that extruded lithium foil can be joined to the membrane by pressing the foil against the Ag layer.
Also as noted above, in an alternative embodiment of the invention the first layer may include additional components. For instance, a suitable first layer may include a polymer component to enhance its properties. For example, polymer-iodine complexes like poly(2-vinylpyridine)-iodine (P2VP-I2), polyethylene-iodine, or tetraalkylammonium-iodine can react with Li to form an ionically conductive LiI-based film that is chemically compatible with both an active metal and a second layer material as described herein. Without intending to be bound by theory, it is expected that the use of polymer-iodine charge transfer complexes can lead to formation of composites containing LiI and polymer and having significantly higher ionic conductivity than that for pure LiI. Other halogens may also be used in this manner, for example in bromine complexes.
Referring to
According to this method, a thin layer of polymer may be applied to the second material layer (e.g., conductive glass) using brushing, dipping, or spraying. For example, a conductive glass layer may be coated with a thin (e.g., 0.5 to 2.0 micron, preferably 0.1 to 0.5 micron) layer of P2VP in this way.
One technique for applying an iodine coating is sublimation of crystalline iodine that can be achieved at room temperature (e.g., about 20 to 25° C.) in a reactor placed in the dry box or in a dry room. A sublimed layer of iodine can be made very thin (e.g., 0.05 to 1.0 microns and the rate of sublimation can be adjusted by varying the temperature or distance between the substrate and source of iodine.
Alternatively, high concentrations (e.g., 50 to 100 g/liter of iodine can be dissolved in an organic solvent, such as acetonitrile and n-heptane. Dissolved iodine can be coated on the conductive glass surface by such methods as dip coating, spraying or brushing, among others. In this case, treatment conditions can be easily changed by varying the length of coating treatment and iodine concentrations. Examples of iodine sources for this technique include metal iodides are AgI and PbI2, which are known to be used as the cathode materials in solid-state batteries with Li anode and LiI-based solid electrolyte.
Then, lithium (or other active metal) is contacted with the polymer-iodine complex on the conductive glass (or other second layer material), for example by evaporation or pressing onto the glass coated with this complex. The result is a LiI-containing composite protective barrier layer on the Li anode.
Referring to
Active metal, for example lithium foil, can be coated with a thin layer of polymer (B), for example as described above, and then contacted with the iodine layer on the glass. After assembly, iodine reacts with the polymer layer and, as a result, LiI-containing composite protective barrier layer with reduced impedance is formed.
The following examples provide details illustrating advantageous properties, in particular very low impedance, of composite membrane protective structures in accordance with the present invention on lithium electrodes. These examples are provided to exemplify and more clearly illustrate aspects of the present invention and are in no way intended to be limiting. Example 1
Approximately 0.75 microns of LiPON was RF sputter-deposited onto copper foil samples in a MRC 8671 Sputter Deposition system. Some of the copper foil samples were coated with an additional layer of Cu3N (approximately 0.9 microns) by RF Magnetron sputtering of a copper target in a nitrogen environment. One LiPON/Cu sample was transferred to a vacuum evaporator, and approximately 3 to 7 microns of lithium metal was evaporated directly onto the LiPON surface. Another Cu3N/LiPON/Cu sample was coated with a similar thickness of lithium. The impedance for the unprotected LiPON/Cu sample is shown in
Samples of Li+ conductive glass-ceramic plates were received from OHARA Corporation. Approximately 3 to 7 microns of lithium was evaporated directly onto the OHARA glass-ceramic plate. The deleterious reaction of lithium with the electrolyte is seen in
Although the foregoing invention has been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing both the process and compositions of the present invention. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein.
All references cited herein are incorporated by reference for all purposes.
Visco, Steven J., Nimon, Yevgeniy S., Katz, Bruce D.
| Patent | Priority | Assignee | Title |
| 10087538, | Oct 09 2008 | ENLIGHTEN INNOVATIONS INC | Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides |
| 10147968, | Dec 02 2014 | PolyPlus Battery Company | Standalone sulfide based lithium ion-conducting glass solid electrolyte and associated structures, cells and methods |
| 10158110, | Jul 11 2011 | California Institute of Technology | Separators for electrochemical systems |
| 10164231, | Feb 05 2013 | HRL Laboratories, LLC | Separators for lithium-sulfur batteries |
| 10164289, | Dec 02 2014 | PolyPlus Battery Company | Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods |
| 10170798, | Dec 01 2010 | FIELD UPGRADING USA, INC | Moderate temperature sodium battery |
| 10320033, | Jan 30 2008 | ENLIGHTEN INNOVATIONS INC | Alkali metal ion battery using alkali metal conductive ceramic separator |
| 10529971, | Feb 06 2004 | PolyPlus Battery Company | Safety enhanced li-ion and lithium metal battery cells having protected lithium electrodes with enhanced separator safety against dendrite shorting |
| 10601071, | Dec 22 2015 | PolyPlus Battery Company | Methods of making and inspecting a web of vitreous lithium sulfide separator sheet and lithium electrode assemblies |
| 10629950, | Jul 07 2017 | PolyPlus Battery Company | Encapsulated sulfide glass solid electrolytes and solid-state laminate electrode assemblies |
| 10693117, | Jul 11 2011 | California Institute of Technology | Electrochemical systems with ionically conductive and electronically insulating separator |
| 10707526, | Mar 27 2015 | NEW DOMINION ENTERPRISES INC | All-inorganic solvents for electrolytes |
| 10707531, | Sep 27 2016 | NEW DOMINION ENTERPRISES INC | All-inorganic solvents for electrolytes |
| 10707536, | May 10 2016 | PolyPlus Battery Company | Solid-state laminate electrode assemblies and methods of making |
| 10714724, | Nov 18 2013 | California Institute of Technology | Membranes for electrochemical cells |
| 10833361, | Dec 02 2014 | PolyPlus Battery Company | Standalone sulfide based lithium ion-conducting glass solid electrolyte and associated structures, cells and methods |
| 10840546, | Dec 02 2014 | PolyPlus Battery Company | Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods |
| 10840547, | Jul 07 2017 | PolyPlus Battery Company | Encapsulated sulfide glass solid electrolytes and solid-state laminate electrode assemblies |
| 10854929, | Sep 06 2012 | FIELD UPGRADING USA, INC | Sodium-halogen secondary cell |
| 10862171, | Jul 19 2017 | PolyPlus Battery Company | Solid-state laminate electrode assembly fabrication and making thin extruded lithium metal foils |
| 10868293, | Jul 07 2017 | PolyPlus Battery Company | Treating sulfide glass surfaces and making solid state laminate electrode assemblies |
| 10916753, | Feb 06 2004 | PolyPlus Battery Company | Lithium metal—seawater battery cells having protected lithium electrodes |
| 11171364, | May 10 2016 | PolyPlus Battery Company | Solid-state laminate electrode assemblies and methods of making |
| 11177537, | Nov 18 2013 | California Institute of Technology | Separator enclosures for electrodes and electrochemical cells |
| 11239495, | Jul 07 2017 | PolyPlus Battery Company | Encapsulated sulfide glass solid electrolytes and solid-state laminate electrode assemblies |
| 11271214, | Dec 02 2015 | California Institute of Technology | Three-dimensional ion transport networks and current collectors for electrochemical cells |
| 11271248, | Mar 27 2015 | New Dominion Enterprises, Inc. | All-inorganic solvents for electrolytes |
| 11444270, | Jul 07 2017 | PolyPlus Battery Company | Treating sulfide glass surfaces and making solid state laminate electrode assemblies |
| 11527802, | Jul 11 2011 | California Institute of Technology | Electrochemical systems with ionically conductive and electronically insulating separator |
| 11631889, | Jan 15 2020 | PolyPlus Battery Company | Methods and materials for protection of sulfide glass solid electrolytes |
| 11646444, | Dec 02 2014 | PolyPlus Battery Company | Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods |
| 11646445, | Dec 02 2014 | PolyPlus Battery Company | Standalone sulfide based lithium ion-conducting glass solid electrolyte and associated structures, cells and methods |
| 11646472, | Feb 06 2004 | PolyPlus Battery Company | Making lithium metal—seawater battery cells having protected lithium electrodes |
| 11749834, | Dec 02 2014 | PolyPlus Battery Company | Methods of making lithium ion conducting sulfide glass |
| 11817569, | Jul 07 2017 | PolyPlus Battery Company | Treating sulfide glass surfaces and making solid state laminate electrode assemblies |
| 11876174, | Jan 15 2020 | PolyPlus Battery Company | Methods and materials for protection of sulfide glass solid electrolytes |
| 11894562, | Dec 02 2015 | California Institute of Technology | Three-dimensional ion transport networks and current collectors for electrochemical cells |
| 7608178, | Nov 10 2003 | PolyPlus Battery Company | Active metal electrolyzer |
| 7666233, | Oct 14 2003 | PolyPlus Battery Company | Active metal/aqueous electrochemical cells and systems |
| 7781108, | Nov 10 2003 | PolyPlus Battery Company | Active metal fuel cells |
| 7829212, | Feb 06 2004 | PolyPlus Battery Company | Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture |
| 7838144, | Oct 15 2002 | PolyPlus Battery Company | Protective composite battery separator and electrochemical device component with red phosphorus |
| 7998626, | Nov 10 2003 | PolyPlus Battery Company | Active metal fuel cells |
| 8012621, | Nov 26 2007 | FIELD UPGRADING USA, INC | Nickel-metal hydride battery using alkali ion conducting separator |
| 8012633, | Oct 13 2006 | FIELD UPGRADING USA, INC | Advanced metal-air battery having a ceramic membrane electrolyte |
| 8048571, | Oct 14 2003 | PolyPlus Battery Company | Active metal / aqueous electrochemical cells and systems |
| 8088270, | Nov 27 2007 | ENLIGHTEN INNOVATIONS INC | Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides |
| 8114171, | Oct 15 2002 | PolyPlus Battery Company | In situ formed ionically conductive membranes for protection of active metal anodes and battery cells |
| 8159192, | Nov 26 2007 | FIELD UPGRADING USA, INC | Method for charging a nickel-metal hydride battery |
| 8182943, | Dec 19 2005 | PolyPlus Battery Company | Composite solid electrolyte for protection of active metal anodes |
| 8202649, | Oct 14 2003 | PolyPlus Battery Company | Active metal/aqueous electrochemical cells and systems |
| 8216722, | Nov 27 2007 | FIELD UPGRADING USA, INC | Solid electrolyte for alkali-metal-ion batteries |
| 8293398, | Feb 06 2004 | PolyPlus Battery Company | Protected active metal electrode and battery cell with ionically conductive protective architecture |
| 8323817, | Sep 12 2008 | FIELD UPGRADING USA, INC | Alkali metal seawater battery |
| 8323820, | Jun 16 2008 | PolyPlus Battery Company | Catholytes for aqueous lithium/air battery cells |
| 8334075, | Dec 19 2005 | PolyPlus Battery Company | Substantially impervious lithium super ion conducting membranes |
| 8361664, | Nov 10 2003 | PolyPlus Battery Company | Protected lithium electrode fuel cell system incorporating a PEM fuel cell |
| 8389147, | Jun 16 2008 | PolyPlus Battery Company | Hydrogels for aqueous lithium/air battery cells |
| 8445136, | Sep 02 2005 | PolyPlus Battery Company | Lithium/sulfur battery with hermetically sealed anode |
| 8455131, | Jun 16 2008 | PolyPlus Battery Company | Cathodes and reservoirs for aqueous lithium/air battery cells |
| 8481195, | Apr 14 2010 | HRL Laboratories, LLC | Lithium battery structures |
| 8501339, | Feb 06 2004 | PolyPlus Battery Company | Protected lithium electrodes having a polymer electrolyte interlayer and battery cells thereof |
| 8652686, | Dec 19 2005 | PolyPlus Battery Company | Substantially impervious lithium super ion conducting membranes |
| 8652692, | Nov 23 2005 | PolyPlus Battery Company | Li/Air non-aqueous batteries |
| 8658304, | Jun 16 2008 | PolyPlus Battery Company | Catholytes for aqueous lithium/air battery cells |
| 8673477, | Jun 16 2008 | PolyPlus Battery Company | High energy density aqueous lithium/air-battery cells |
| 8691444, | Sep 02 2005 | PolyPlus Battery Company | Lithium battery with hermetically sealed anode |
| 8709679, | Nov 10 2003 | PolyPlus Battery Company | Active metal fuel cells |
| 8722221, | Nov 26 2007 | FIELD UPGRADING USA, INC | Method of discharging a nickel-metal hydride battery |
| 8735003, | Jun 16 2010 | Alliance for Sustainable Energy, LLC | Lithium-ion batteries having conformal solid electrolyte layers |
| 8771855, | Aug 11 2010 | FIELD UPGRADING USA, INC | Alkali metal aqueous battery |
| 8771879, | Sep 05 2007 | ENLIGHTEN INNOVATIONS INC | Lithium—sulfur battery with a substantially non-porous lisicon membrane and porous lisicon layer |
| 8778522, | Oct 15 2002 | PolyPlus Battery Company | Protected lithium electrodes based on sintered ceramic or glass ceramic membranes |
| 8828573, | Nov 15 2011 | PolyPlus Battery Company | Electrode structures for aqueous electrolyte lithium sulfur batteries |
| 8828574, | Nov 15 2011 | PolyPlus Battery Company | Electrolyte compositions for aqueous electrolyte lithium sulfur batteries |
| 8828575, | Nov 15 2011 | PolyPlus Battery Company | Aqueous electrolyte lithium sulfur batteries |
| 8859141, | Nov 05 2009 | FIELD UPGRADING USA, INC | Solid-state sodium-based secondary cell having a sodium ion conductive ceramic separator |
| 8932771, | May 03 2012 | PolyPlus Battery Company | Cathode architectures for alkali metal / oxygen batteries |
| 9123941, | Feb 06 2004 | PolyPlus Battery Company | Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture |
| 9130198, | Aug 09 2005 | PolyPlus Battery Company | Compliant seal structures for protected active metal anodes |
| 9136568, | Oct 14 2003 | PolyPlus Battery Company | Protected lithium electrodes having tape cast ceramic and glass-ceramic membranes |
| 9166263, | Jul 06 2012 | Samsung Electronics Co., Ltd. | Anode for lithium air battery and lithium air battery including the anode |
| 9209445, | Nov 26 2007 | FIELD UPGRADING USA, INC | Nickel-metal hydride/hydrogen hybrid battery using alkali ion conducting separator |
| 9252455, | Apr 14 2010 | HRL Laboratories, LLC | Lithium battery structures employing composite layers, and fabrication methods to produce composite layers |
| 9287573, | Jun 29 2007 | PolyPlus Battery Company | Lithium battery cell with protective membrane having a garnet like structure |
| 9362538, | Oct 15 2002 | PolyPlus Battery Company | Advanced lithium ion batteries based on solid state protected lithium electrodes |
| 9368775, | Feb 06 2004 | PolyPlus Battery Company | Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers |
| 9379368, | Jul 11 2011 | California Institute of Technology | Electrochemical systems with electronically conductive layers |
| 9419299, | Oct 14 2003 | PolyPlus Battery Company | Battery cells with lithium ion conducting tape-cast ceramic, glass and glass-ceramic membranes |
| 9478825, | Apr 14 2010 | HRL Laboratories, LLC | Lithium battery structures employing composite layers, and fabrication methods to produce composite layers |
| 9502735, | Apr 14 2010 | HRL Laboratories, LLC | Fabrication methods to produce lithium battery structures with composite layers |
| 9601779, | Oct 14 2003 | PolyPlus Battery Company | Battery cells with lithium ion conducting tape-cast ceramic, glass and glass-ceramic membranes |
| 9627691, | Feb 07 2013 | ADA Technologies, Inc | Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same |
| 9627727, | Jul 22 2014 | Toyota Jidosha Kabushiki Kaisha | Lithium-air battery with cathode separated from free lithium ion |
| 9660265, | Nov 15 2011 | PolyPlus Battery Company | Lithium sulfur batteries and electrolytes and sulfur cathodes thereof |
| 9660311, | Aug 19 2011 | PolyPlus Battery Company | Aqueous lithium air batteries |
| 9666850, | Feb 06 2004 | PolyPlus Battery Company | Safety enhanced Li-ion and lithium metal battery cells having protected lithium electrodes with enhanced separator safety against dendrite shorting |
| 9831043, | Sep 09 2010 | California Institute of Technology | Electrochemical energy storage systems and methods |
| 9905860, | Jun 28 2013 | PolyPlus Battery Company | Water activated battery system having enhanced start-up behavior |
| 9954213, | Jul 11 2011 | California Institute of Technology | Electrochemical systems with at least one electronically and ionically conductive layer |
| 9991492, | Nov 18 2013 | California Institute of Technology | Separator enclosures for electrodes and electrochemical cells |
| Patent | Priority | Assignee | Title |
| 3607417, | |||
| 3625769, | |||
| 3703415, | |||
| 3912536, | |||
| 3976509, | Apr 04 1975 | Lockheed Missiles & Space Company, Inc | Electrolyte compositions |
| 4007057, | Dec 29 1975 | Lockheed Missiles & Space Company, Inc | Cell comprising an alkali metal and aqueous electrolyte |
| 4091182, | Mar 01 1976 | General Electric Company | Sealed lithium electrochemical cell with sodium beta-alumina electrolyte |
| 4162202, | Mar 08 1976 | DURACELL INC , A CORP OF DEL | Means for improving contact between Li and the anode current collector |
| 4163084, | Jul 27 1978 | Lockheed Missiles & Space Company, Inc. | Electrochemically stable cathode |
| 4210707, | Nov 20 1978 | General Electric Company | Sealed lithium-type electrochemical cell |
| 4402995, | Jan 28 1982 | RAYOVAC CORPORATION, 601 RAYOVAC DR , MADISON, WI 53711, A WI CORP | Treatment of lithium anodes |
| 4405416, | Jul 18 1980 | Molten salt lithium cells | |
| 4414293, | Sep 20 1982 | The United States of America as represented by the United States | Parasitic corrosion resistant anode for use in metal/air or metal/O2 cells |
| 4833048, | Mar 31 1988 | Regents of the University of California, The | Metal-sulfur type cell having improved positive electrode |
| 4917974, | Apr 14 1989 | Regents of the University of California, The | Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same |
| 4981672, | Jun 27 1983 | VOLTAIX, LLC | Composite coating for electrochemical electrode and method |
| 4985317, | Nov 30 1988 | JSR Corporation | Lithium ion-conductive solid electrolyte containing lithium titanium phosphate |
| 5100523, | Dec 17 1990 | Ford Motor Company | Use of amorphous carbon to promote adhesion between electroactive polymer films and conductive substrates |
| 5108856, | May 15 1986 | ENZON LABS INC ; Genex Corporation | Electrolyte compositions and methods |
| 5162175, | Oct 13 1989 | Regents of the University of California, The | Cell for making secondary batteries |
| 5166011, | Nov 07 1990 | Alupower, Inc. | Process for forming an argentic oxide containing bipolar electrode and product produced thereby and deferred actuated battery assembly employing same |
| 5213908, | Sep 26 1991 | The United States of America as represented by the Administrator of the | Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen |
| 5314765, | Oct 14 1993 | Martin Marietta Energy Systems, Inc. | Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method |
| 5336384, | Nov 14 1991 | The Dow Chemical Company | Membrane-electrode structure for electrochemical cells |
| 5338625, | Jul 29 1992 | Martin Marietta Energy Systems, Inc.; MARTIN MARIETTA ENERGY SYSTEMS, INC , A DE CORP | Thin film battery and method for making same |
| 5342710, | Mar 30 1993 | Valence Technology, Inc.; Valence Technology, Inc | Lakyer for stabilization of lithium anode |
| 5387479, | Jun 16 1993 | Valence Technology, Inc.; Valence Technology, Inc | Electrodes for rechargeable lithium batteries |
| 5409786, | Feb 05 1993 | Eveready Battery Company, Inc | Inactive electrochemical cell having an ionically nonconductive polymeric composition activated by electrolyte salt solution |
| 5427873, | Sep 14 1990 | ENSER CORPORATION, THE, A CORP OF ALABAMA | Lithium-water battery |
| 5455126, | Jul 29 1992 | Martin Marietta Energy Systems, Inc. | Electra-optical device including a nitrogen containing electrolyte |
| 5506068, | Mar 01 1994 | TADIRAN BATTERIES LTD | Non-aqueous safe secondary cell |
| 5510209, | Jan 05 1995 | EIC Laboratories, Inc. | Solid polymer electrolyte-based oxygen batteries |
| 5512147, | Jul 29 1992 | Martin Marietta Energy Systems, Inc. | Method of making an electrolyte for an electrochemical cell |
| 5516598, | Jul 28 1994 | POLYPLUS BATTERY COMPANY, INC | Secondary cell using organosulfur/metal charge transfer materials as positive electrode |
| 5523179, | Nov 23 1994 | POLY-PLUS BATTERY COMPANY | Rechargeable positive electrode |
| 5525442, | Sep 14 1990 | ENSER CORPORATION, THE, A CORP OF ALABAMA | Alkali metal battery |
| 5532077, | Nov 23 1994 | PolyPlus Battery Company, Inc. | Rechargeable positive electrode |
| 5567210, | Jul 29 1992 | Martin Marietta Energy Systems, Inc. | Method for making an electrochemical cell |
| 5569520, | Jan 12 1994 | Martin Marietta Energy Systems, Inc. | Rechargeable lithium battery for use in applications requiring a low to high power output |
| 5582623, | Nov 23 1994 | PolyPlus Battery Company, Inc. | Methods of fabricating rechargeable positive electrodes |
| 5597660, | Jul 29 1992 | Martin Marietta Energy Systems, Inc. | Electrolyte for an electrochemical cell |
| 5612152, | Jan 12 1994 | Martin Marietta Energy Systems, Inc. | Rechargeable lithium battery for use in applications requiring a low to high power output |
| 5648187, | Feb 16 1994 | Sion Power Corporation | Stabilized anode for lithium-polymer batteries |
| 5652068, | Nov 14 1995 | ENSER CORPORATION, THE, A CORP OF ALABAMA | Metal-air battery with improved air supply |
| 5665481, | Nov 14 1995 | ENSER CORPORATION, THE, A CORP OF ALABAMA | Metal-air battery |
| 5686201, | Nov 23 1994 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC ; PolyPlus Battery Company | Rechargeable positive electrodes |
| 5696201, | Apr 06 1992 | Matec Holding AG | Sound and heat insulation having little odor |
| 5702995, | Nov 15 1995 | Kabushiki Kaisha Ohara | Lithium ion conductive glass-ceramics |
| 5814420, | Nov 23 1994 | PolyPlus Battery Company, Inc. | Rechargeable positive electrodes |
| 5882812, | Jan 14 1997 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC ; PolyPlus Battery Company | Overcharge protection systems for rechargeable batteries |
| 5961672, | Feb 16 1994 | Sion Power Corporation | Stabilized anode for lithium-polymer batteries |
| 6017651, | Nov 23 1994 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC ; PolyPlus Battery Company | Methods and reagents for enhancing the cycling efficiency of lithium polymer batteries |
| 6025094, | Nov 23 1994 | PolyPlus Battery Company, Inc. | Protective coatings for negative electrodes |
| 6030720, | Nov 23 1994 | PolyPlus Battery Co., Inc. | Liquid electrolyte lithium-sulfur batteries |
| 6030909, | Oct 28 1996 | Kabushiki Kaisha Ohara | Lithium ion conductive glass-ceramics and electric cells and gas sensors using the same |
| 6068950, | Nov 19 1997 | GREATBATCH, LTD NEW YORK CORPORATION | Organic phosphate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| 6096447, | Nov 05 1997 | GREATBATCH, LTD NEW YORK CORPORATION | Phosphonate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| 6110236, | Sep 11 1998 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC | Method of preparing electrodes having evenly distributed component mixtures |
| 6146787, | Nov 11 1998 | Battelle Energy Alliance, LLC | Solid polymer battery electrolyte and reactive metal-water battery |
| 6165644, | Nov 23 1994 | PolyPlus Battery Company, Inc. | Methods and reagents for enhancing the cycling efficiency of lithium polymer batteries |
| 6183901, | Dec 17 1998 | Optodot Corporation | Protective coating for separators for electrochemical cells |
| 6198701, | Sep 03 1998 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC | Electrochemical timer |
| 6200701, | Jan 25 1999 | GREATBATCH, LTD NEW YORK CORPORATION | Phosphonate additives for nonaqueous electrolyte in rechargeable cells |
| 6200704, | Sep 01 1998 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC ; PolyPlus Battery Company | High capacity/high discharge rate rechargeable positive electrode |
| 6203942, | Oct 22 1998 | GREATBATCH, LTD NEW YORK CORPORATION | Phosphate additives for nonaqueous electrolyte rechargeable electrochemical cells |
| 6210832, | Sep 01 1998 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC ; PolyPlus Battery Company | Mixed ionic electronic conductor coatings for redox electrodes |
| 6214061, | May 01 1998 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC | Method for forming encapsulated lithium electrodes having glass protective layers |
| 6225002, | Feb 05 1999 | PolyPlus Battery Company, Inc. | Dioxolane as a proctector for lithium electrodes |
| 6228527, | Mar 02 1999 | NAVY, SECRETARY OF THE, UNITED STATES OF AMERICA AS REPRESENTED BY | Magnesium solution phase catholyte seawater electrochemical system |
| 6248481, | Jan 14 1997 | PolyPlus Battery Company, Inc. | Overcharge protection systems for rechargeable batteries |
| 6274269, | Nov 19 1997 | GREATBATCH, LTD NEW YORK CORPORATION | Method for reducing voltage delay in alkali metal electrochemical cells activated with a nonaqueous electrolyte having a phosphate additive |
| 6280598, | Mar 13 1995 | Magnesium Technology Limited | Anodization of magnesium and magnesium based alloys |
| 6315881, | Nov 15 1995 | Kabushiki Kaisha Ohara | Electric cells and gas sensors using alkali ion conductive glass ceramic |
| 6358643, | Nov 23 1994 | PolyPlus Battery Company; POLYPLUS BATTERY COMPANY, INC | Liquid electrolyte lithium-sulfur batteries |
| 6358651, | Feb 26 1999 | EVIONYX, INC | Solid gel membrane separator in rechargeable electrochemical cells |
| 6376123, | Nov 23 1994 | PolyPlus Battery Company | Rechargeable positive electrodes |
| 6391492, | Apr 05 1992 | Canon Kabushiki Kaisha | Secondary battery |
| 6402795, | Feb 18 1998 | PolyPlus Battery Company, Inc.; POLYPLUS BATTERY COMPANY, INC | Plating metal negative electrodes under protective coatings |
| 6413284, | Nov 01 1999 | POLYPLUS BATTERY COMPANY, INC | Encapsulated lithium alloy electrodes having barrier layers |
| 6413285, | Nov 01 1999 | PolyPlus Battery Company | Layered arrangements of lithium electrodes |
| 6432584, | May 01 1998 | PolyPlus Battery Company | Method for forming encapsulated lithium electrodes having glass protective layers |
| 6475677, | Apr 30 1999 | Kabushiki Kaisha Ohara | Glass-ceramic composite electrolyte and lithium secondary cell |
| 6485622, | Sep 27 1999 | Kabushiki Kaisha Ohara | Lithium ion conductive glass-ceramics and electric cells and gas sensors using the same |
| 6489055, | Jun 25 1999 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
| 6495285, | Jan 25 1999 | GREATBATCH, LTD NEW YORK CORPORATION | Phosphonate additives for nonaqueous electrolyte in rechargeable electrochemical cells |
| 6511772, | Jan 17 2001 | GREATBATCH, LTD NEW YORK CORPORATION | Electrochemical cell having an electrode with a phosphate additive in the electrode active mixture |
| 6537698, | Mar 21 2001 | GREATBATCH, LTD NEW YORK CORPORATION | Electrochemical cell having an electrode with a phosphonate additive in the electrode active mixture |
| 6537701, | Sep 03 1998 | PolyPlus Battery Company, Inc. | Coated lithium electrodes |
| 6632573, | Feb 20 2001 | PolyPlus Battery Company | Electrolytes with strong oxidizing additives for lithium/sulfur batteries |
| 6723140, | Feb 18 1998 | Plating metal negative electrodes under protective coatings | |
| 6737197, | Nov 01 1999 | PolyPlus Battery Company | Encapsulated lithium alloy electrodes having barrier layers |
| 6797428, | Nov 23 1999 | Sion Power Corporation | Lithium anodes for electrochemical cells |
| 6911280, | Dec 21 2001 | PolyPlus Battery Company | Chemical protection of a lithium surface |
| 6955866, | Sep 03 1998 | PolyPlus Battery Company | Coated lithium electrodes |
| 6991662, | Sep 10 2001 | PolyPlus Battery Company | Encapsulated alloy electrodes |
| 7070632, | Jul 25 2001 | PolyPlus Battery Company | Electrochemical device separator structures with barrier layer on non-swelling membrane |
| 20010041294, | |||
| 20020012846, | |||
| 20020034688, | |||
| 20020102465, | |||
| 20040197641, | |||
| 20050100793, | |||
| 20060078790, | |||
| EP111214, | |||
| EP689260, | |||
| EP838441, | |||
| EP875951, | |||
| EP1162675, | |||
| JP55081471, | |||
| JP9320645, | |||
| WO2005038953, | |||
| WO2005038962, | |||
| WO250933, | |||
| WO9957770, |
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